Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide

ABSTRACT

A composition comprising a copolymer having repeating units in any sequence of Formula I 
     
       
         
         
             
             
         
       
     
     wherein
         R f  is a straight or branched perfluoroalkyl group having from about 1 to about 20 carbon atoms, or a mixture thereof, which is optionally interrupted by at least one oxygen atom,   X 3  is oxygen or X 1 ,   each X 1  is independently an organic divalent linking group having from about 1 to about 20 carbon atoms, optionally containing an oxygen, nitrogen, or sulfur, or a combination thereof,   G is F or CF 3 ,   A is an amide,   j is zero or positive integer,   X 2  is an organic linking group,   Y is O, N or S,   h is zero when Y is N, and h is one when Y is O or S,   Z is H, a straight or branched alkyl group having from about 1 to about 4 carbon atoms, or halide,   B is H or       

     
       
         
         
             
             
         
       
     
     wherein
         R f , X 1 , X 3 , G, A, and j are as defined above, provided that when B is H, j is a positive integer,   m is a positive integer,   q is zero or a positive integer when Y is O, and q is a positive integer when Y is N or S,   p is zero or a positive integer when Y is O, and p is a positive integer when Y is N or S,   each W is independently various copolymer units.

BACKGROUND OF THE INVENTION

Various compositions are known to be useful as treating agents toprovide surface effects to substrates. Surface effects includerepellency to moisture, soil, and stains, and other effects, which areparticularly useful for fibrous substrates and other substrates such ashard surfaces. Many such treating agents are fluorinated polymers orcopolymers.

Most commercially available fluorinated polymers useful as treatingagents for imparting repellency to substrates contain predominantlyeight or more carbons in the perfluoroalkyl chain to provide the desiredrepellency properties. Honda et al, in Macromolecules, 2005, 38,5699-5705 teach that for perfluoroalkyl chains of greater than 8carbons, orientation of the R_(f) groups is maintained in a parallelconfiguration while for such chains having less than 6 carbons,reorientation occurs, which decreases surface properties such as contactangle. Thus shorter chain perfluoroalkyls have traditionally not beensuccessful commercially.

Various attempts have been made to improve particular surface effectsand to increase the fluorine efficiency; i.e., boost the efficiency orperformance of treating agents so that lesser amounts of the expensivefluorinated polymer are required to achieve the same level ofperformance or have better performance using the same level of fluorine.It is desirable to reduce the chain length of the perfluoroalkyl groupsthereby reducing the amount of fluorine present, while still achievingthe same or superior surface effects. U.S. Pat. No. 3,576,018 disclosesfluorinated acrylamide monomers useful as oil and water repellent agentscontaining a perfluoroalkyl or fluorinated isoalkoxyalkyl having 3 to 17carbon atoms. No polymers or copolymers are disclosed.

There is a need for polymer compositions which significantly improve therepellency and stain resistance of fluorinated polymer treating agentsfor fibrous substrates and hard surface substrates while using lowerlevels of fluorine. The present invention provides such compositions.

SUMMARY OF THE INVENTION

The present invention comprises a composition comprising a copolymerhaving repeating units in any sequence of Formula I

wherein

R_(f) is a straight or branched perfluoroalkyl group having from about 1to about 20 carbon atoms, or a mixture thereof, which is optionallyinterrupted by at least one oxygen atom,

X³ is oxygen or X¹,

each X¹ is independently an organic divalent linking group having fromabout 1 to about 20 carbon atoms, optionally containing an oxygen,nitrogen, or sulfur, or a combination thereof,

G is F or CF₃,

A is an amide,

j is zero or positive integer,

X² is an organic linking group,

Y is O, N, or S,

h is zero when Y is N, and h is one when Y is O or S,

Z is H, a straight or branched alkyl group having from about 1 to about4 carbon atoms, or halide,

B is H or

wherein

R_(f), X¹, X³, G, A, and j are as defined above, provided that when B isH, j is a positive integer,

m is a positive integer,

q is zero or a positive integer when Y is O, and q is a positive integerwhen Y is N or S,

p is zero or a positive integer when Y is O, and p is a positive integerwhen Y is N or S, and

each W is independently

-   -   or [R¹—X¹—Y—C(O)—C(Z)-CH₂],        wherein

X¹, Y, and Z are as defined above,

Rx is C(O)O(R¹), C(O)N(R²)₂, OC(O)(R¹), SO₂(R¹), C₆(R³)₅, O(R¹), halide,or R¹;

each R¹ is independently H, C_(n)H_(2n+1), C_(n)H_(2n)—CH(O)CH₂,[CH₂CH₂O]_(i)R⁴, [C_(n)C_(2n)]N(R⁴)₂ or [C_(n)H_(2n)]C_(n)F_(2n+1),

n is 1 to 40,

R⁴ is H or C_(s)H_(2s+1),

s=0 to 40,

i=1 to 200,

each R² is independently H, or C_(t)H_(2t+1) wherein t is 1 to 20,

each R³ is independently H, COOR¹, halogen, N(R¹)₂, OR¹, SO₂NHR¹,CH═CH₂, or SO₃M, wherein R¹ is as defined above, and

M is H, alkali metal salt, alkaline earth metal salt, or ammonium.

The present invention further comprises a composition comprising Formula2

wherein

R_(f), X¹, X³, G, j, A, Y, X², h, B, and Z are each defined as forFormula 1 above, provided that when Y is N or S, j is a positiveinteger.

The present invention further comprises a composition comprising Formula3.

wherein

R_(f), X¹, X³, G, j, A, B, X², and h are each defined as in Formula 2above, and E is selected from the group consisting of hydroxyl, amine,halogen, and thiol, provided that h is zero when E is amine, and h isone when E is other than amine.

The present invention further comprises a method of providing waterrepellency and oil repellency to a substrate comprising contacting saidsubstrate with a composition of Formula 1 as defined above.

The present invention further comprises a substrate to which has beenapplied a composition of Formula 1 as defined above.

DETAILED DESCRIPTION

All trademarks are denoted herein by capitalization. In all instancesherein, the term “(meth)acrylate” is used to denote both acrylate ormethacrylate. The term “(meth)acryloyl chloride” is used to denote bothacryloyl chloride and methacryloyl chloride. The term “(meth)acrylamide”is used to denote both acrylamide or methacrylamide.

The present invention comprises a copolymer having repeating units inany sequence of Formula 1

wherein

R_(f) is a straight or branched perfluoroalkyl group having from about 1to about 20 carbon atoms, or a mixture thereof, which is optionallyinterrupted by at least one oxygen atom,

X³ is oxygen or X¹,

each X¹ is independently an organic divalent linking group having fromabout 1 to about 20 carbon atoms, optionally containing an oxygen,nitrogen, or sulfur, or a combination thereof,

G is F or CF₃,

A is an amide,

j is zero or positive integer, provided that when B is H, j is apositive integer,

X² is an organic linking group,

Y is O, N or S,

h is zero when Y is N, and h is one when Y is O or S,

Z is H, a straight or branched alkyl group having from about 1 to about4 carbon atoms, or halide,

B is H or

wherein

R_(f), X¹, X³, G, j, and A are as defined above, provided that when B isH, j is a positive integer,

m is a positive integer,

q is zero or a positive integer when Y is O, and q is a positive integerwhen Y is N or S,

p is zero or a positive integer when Y is O, and p is a positive integerwhen Y is N or S,

each W is independently

or [R¹—X¹—Y—C(O)—CH₂Z],

wherein

X¹, Y, and Z are as defined above,

Rx is C(O)O(R¹), C(O)N(R²)₂, OC(O)(R¹), SO₂(R¹), C₆(R³)₅, O(R¹), halide,or R¹;

each R¹ is independently H, C_(n)H_(2n+1), C_(n)H_(2n)—CH(O)CH₂,[CH₂CH₂O]_(i)R⁴, [C_(n)C_(2n)]N(R⁴)₂ or [C_(n)H_(2n)]C_(n)F_(2n+1),

n is 1 to 40,

R⁴ is H or C_(s)H_(2s+1),

s=0 to 40,

i=1 to 200,

each R² is independently H, or C_(t)H_(2t+1) wherein t is 1 to 20,

each R³ is independently H, COOR¹, halogen, N(R¹)₂, OR¹, SO₂NHR¹,CH═CH₂, or SO₃M, and

M is H, alkali metal salt, alkaline earth metal salt, or ammonium.

Preferably R_(f) is a straight or branched perfluoroalkyl group havingfrom about 1 to about 18 carbon atoms or a mixture thereof. Morepreferably R_(f) is from about 1 to about 12 carbon atoms, or a mixturethereof. More preferably R_(f) is from about 1 to about 6 carbon atoms,or a mixture thereof.

A is amide. In particular, A is —CONR⁵— or —NR⁵C(O)— wherein R⁵ is H oralkyl.

Examples of suitable linking groups X¹ include straight chain, branchedchain or cyclic alkylene, phenyl, arylene, arylalkylene, sulfonyl,sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene(—NR⁵CONR⁵— wherein R⁵ is H or alkyl), and combinations thereof such assulfonamidoalkylene.

The copolymers of Formula 1 are prepared by polymerization offluorinated amide-containing acrylic monomers, alkyl(meth)acrylatemonomers and optionally other monomers. The copolymers of Formula 1 areprepared by reacting fluorinated (meth)acrylate or nonfluorinated(meth)acrylate with a fluorinated amide-containing fluorinated acrylicmonomer of Formula 2:

wherein

R_(f), X¹, X³, G, j, A, B, Y, X², h, and Z are each defined as forFormula 1 above, provided that, when Y is N or S, j is a positiveinteger.

The fluorinated amide-containing acrylic monomer of Formula 2, used inthe preparation of the copolymer of Formula 1, is prepared by contactingacrylic acid, acrylate ester, or acryloyl chloride with a fluorochemicalof Formula 3:

wherein

R_(f), X¹, X³, G, j, A, X², and h are each defined as in Formula 2above, and E is selected from the group consisting of hydroxyl, amine,halogen, and thiol, provided that h is zero when E is amine, and h isone when E is other than amine. E is preferably hydroxyl or amine.

The preferred conditions for the reaction are at a temperature of fromabout 0° C. and about 60° C. Suitable solvents include tetrahydrofuran,methyl isobutyl ketone, acetone or ethyl acetate. A tertiary amine isused as a base to scavenge any acid chloride formed during the reaction.

The compound of Formula 3 is prepared by reaction between aperfluorinated ester (prepared according to reported methods in U.S.Pat. No. 6,054,615 and U.S. Pat. No. 6,376,705 each herein incorporatedby reference) with a triamine or diamine alcohol with or withoutsolvent. The conditions of this reaction are dependent on structure ofthe ester. The reaction of alpha, alpha-difluorosubstituted ester withdiamine is conducted at a temperature of from about 5° C. to about 35°C. Suitable solvents for this reaction include tetrahydrofuran, methylisobutyl ketone, acetone, CHCl₃, CH₂Cl₂, or ether. The reaction of esterwithout alpha-fluorine substitution with diamine is conducted at atemperature of from about 90° C. to about 160° C., preferably at betweenabout 100° C. to about 140° C. Preferably no solvent is employed forthis reaction, but suitable solvents include chlorobenzene,dimethylformamide, or 2-methoxyethyl ether.

The compound of Formula 3 is also prepared by reaction between aperfluorinated acyl fluoride with a diamine alcohol or amine alcohol.This reaction is conducted at a temperature of from about −30° C. toabout 40° C., preferably at between about 5° C. to about 25° C. Suitablesolvents for this reaction include tetrahydrofuran, methyl isobutylketone, acetone, CHCl₃, CH₂Cl₂, or 2-methoxyethyl ether, diethyl ether.

The fluorinated amide-containing fluorinated acrylic monomer of Formula2 of the present invention is then polymerized with fluorinated(meth)acrylate or nonfluorinated (meth)acrylate to prepare the copolymerof Formula 1.

The nonfluorinated (meth)acrylate monomers suitable for use in thepreparation of the copolymer of Formula 1 of the present inventioncomprise alkyl (meth)acrylates in which the alkyl group is a straight orbranched chain containing 1 to about 20 carbon atoms, or mixturesthereof, preferably from about 1 to about 18 carbon atoms. The C₁-C₂₀alkyl (meth)acrylates (linear or branched) are exemplified by, but notlimited to, alkyl (meth)acrylates where the alkyl group is methyl,ethyl, propyl, butyl, isoamyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl,decyl, isodecyl, lauryl, cetyl, or stearyl. The preferred examples are2-ethylhexyl acrylate, lauryl acrylate and stearyl acrylate.

Additional optional monomers can also be used in the polymerizationreaction to prepare the copolymers of Formula 1 containing additionalrepeating units. These optional monomers include N-methylol(meth)acrylates, hydroxyalkyl (meth)acrylates, alkyloxy(meth)acrylates,fluorinated (meth)acrylates, glycidyl (meth)acrylates, stearyl acrylate,aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamide,vinyl acetate, vinyl stearate, alkyl vinyl sulfone, styrene, vinylbenzoic acid, alkyl vinyl ether, maleic anhydride, vinylidene chloride,vinyl chloride, and olefin.

Optional N-methylol monomers are exemplified by N-methylol acrylamideand N-methylol methacrylamide. The optional hydroxyalkyl (meth)acrylateshave alkyl chain lengths in range between about 2 and about 4 carbonatoms, and are exemplified by 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate. The optional alkyloxy(meth)acrylates also have alkyl chainlengths in range between about 2 and about 4 carbon atoms, and containbetween 1 and about 12 oxyalkylene units per molecule, preferablybetween about 4 and about 10 oxyalkylene units per molecule, and mostpreferably between about 6 and about 8 oxyalkylene units per molecule,as determined by gas chromatography/mass spectrometry. Specific examplesof the poly(oxyalkylene)(meth)acrylates are exemplified by, but notlimited to, the reaction product of 2-hydroxyethyl methacrylate ethyleneoxide. The reaction with nine moles of ethylene oxide yields2-hydroxyethyl methacrylate/9-ethylene oxide adduct, and the reactionwith six moles of ethylene oxide yields 2-hydroxyethylmethacrylate/6-ethylene oxide adduct. Other optional nonfluorinatedmonomers can be styrene, maleic anhydride, and vinylidene chloride. Whensuch optional monomers are present, polymerization processes employedare conventional ones known to those skilled in the art.

The fluorinated copolymers of Formula 1 of this invention are preparedin organic solvent by free radical initiated polymerization of a mixtureof fluorinated amide-containing acrylic monomers of Formula 2 with a(meth)acrylate, and, any of the optional monomers listed above. Thefluorinated copolymers of this invention are made by agitating themonomers described above in organic solvent in a suitable reactionvessel which is equipped with an agitation device and an externalheating and cooling device. A free radical initiator is added and thetemperature rose to from about 40° to about 60° C. A polymerizationregulator or chain transfer agent may be added to control molecularweight of the resultant polymer. The polymerization initiator isexemplified by [2,2′-azobis(2,4-dimethylpentanenitrile)]. Theseinitiators are sold by E. I. du Pont de Nemours and Company, Wilmington,Del., commercially under the name of “VAZO”. An example of thepolymerization regulator or chain transfer agent is dodecylmercaptan.Suitable organic solvents useful in the preparation of the copolymers ofFormula 1 of the present invention include tetrahydrofuran, acetone,methyl isobutyl ketone, isopropanol, ethyl acetate, and mixtures ofthem. Tetrahydrofuran is preferred. The reaction is conducted under aninert gas, such as nitrogen, to the exclusion of oxygen. The solutioncan be retained for dilution and application to the substrate.Alternatively, the polymer can be isolated by precipitation withmethanol, then dissolves in suitable solvent, such as tetrahydrofuranfor application to the substrate. The product of the reaction is afluorinated amide-containing copolymer of Formula 1.

The fluorinated amide-containing copolymer of Formula 1 can be madeusing from about 25 to about 80 weight percent fluorinatedamide-containing acrylate of Formula 2, from about 1 to about 40 weightpercent (meth)acrylate, and from 0 to about 75 weight percent optionalmonomers.

The resulting fluorinated amide-containing copolymer of Formula 1 isthen poured into water. The collected polymer is dissolved in a solventselected from the groups comprising simple alcohols, ketones ortetrahydrofuran that are suitable as the solvent for final applicationto substrates (hereinafter the “application solvent”). The final productfor application to a substrate is a solution of the fluorinatedamide-containing copolymer of Formula 1.

The present invention further comprises a composition of Formula 2 asdefined above wherein R_(f) is linear. This composition is prepared asdescribed above by contacting acrylic acid, acrylate ester, or acryloylchloride with a fluorochemical of Formula 3 as defined above whereinR_(f) is linear. This composition is useful for the preparation of acomposition of Formula 1 wherein R_(f) is linear.

The present invention further comprises a composition of Formula 3 asdefined above wherein R_(f) is linear. This composition is prepared asdescribed above by the reaction of a triamine or diamine alcohol with aperfluorinated ester wherein the perfluoro group is linear. Thiscomposition is useful for preparing a composition of Formula 2 whereinR_(f) is linear.

The present invention further comprises a method of providing oilrepellency and water repellency to a substrate comprising contacting thefluorinated amide-containing copolymer solutions of Formula 1 of thepresent invention with the substrate. Suitable substrates includefibrous or hard surface substrates as defined below. The contacting isconducted using conventional techniques. The copolymer of Formula 1 iseffectively applied to fibrous substrates by a wide variety of methodsknown to those skilled in the art, such as: padding, spraying, foamingin conjunction with foaming agents, flex-nip, nip, kiss-roll,exhaustion, beck, skein, winch, liquid injection, overflow flood,exhaust in beck dyeing equipment, or continuous exhaust during acontinuous dyeing operation. It is applied by such methods to dyed orundyed substrates. For hard surface substrates application techniquesinclude, for example, by brushes, rollers, paint pads, mats, sponges,combs, hand-operated pump dispensers, compressed air operated sprayguns, electric or electrostatic atomizers, backpack spray applicationequipment, clothes, papers, feathers, styluses, knives, and otherconventional applicator tools. If dipping is used as a method to applythe copolymer, no special equipment is required.

The fluorinated amide-containing copolymer solution of Formula 1 of thisinvention is applied to the substrate as such, or in combination withother optional textile finishes or surface treating agents. Suchoptional additional components include treating agents or finishes toachieve additional surface effects, or additives commonly used with suchagents or finishes. Such additional components comprise compounds orcompositions that provide surface effects such as no iron, easy to iron,shrinkage control, wrinkle free, permanent press, moisture control,softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil repellency, soil release, waterrepellency, oil repellency, odor control, antimicrobial, sun protection,and similar effects. One or more such treating agents or finishes can beapplied to the substrate before, after, or simultaneously with thecopolymer of the present invention. For example for fibrous substrates,when synthetic or cotton fabrics are treated, use of a wetting agent canbe desirable, such as ALKANOL 6112 available from E. I. du Pont deNemours and Company, Wilmington, Del. When cotton or cotton-blendedfabrics are treated, a wrinkle-resistant resin can be used such asPERMAFRESH EFC available from Omnova Solutions, Chester, S.C.

Other additives commonly used with such treating agents or finishes mayalso be present such as surfactants, pH adjusters, cross linkers,wetting agents, wax extenders, and other additives known by thoseskilled in the art. Suitable surfactants include anionic, cationic, andnonionic. Preferred is an anionic surfactant such as sodium laurylsulfonate, available as DUPONOL WAQE from Witco Corporation, Greenwich,Conn. Examples of such finishes or agents include processing aids,foaming agents, lubricants, anti-stains, and the like. The compositionis applied at a manufacturing facility, retailer location, or prior toinstallation and use, or at a consumer location.

Application rates for the fluorinated amide-containing copolymersolution of Formula 1 of the present invention are in the range of fromabout 10 to about 1000 g/m² depending on the substrate porosity. Atreated fibrous substrate typically has a fluorine content of from about0.05% to about 1.0% by weight. Generally, higher levels of fluorineprovide greater oil repellency and water repellency, but becomeeconomically unfeasible. The fluorine loading is optimized dependingupon type of substrate.

The optimal repellent treatment for a given substrate depends on (1) thecharacteristics of the fluorinated copolymer, (2) the characteristics ofthe surface of the substrate, (3) the amount of fluorinated copolymerapplied to the surface, (4) the method of application of the fluorinatedcopolymer onto the surface, and many other factors. Some fluorinatedcopolymer repellents work well on many different substrates and arerepellent to oil, water, and a wide range of other liquids. Otherfluorinated copolymer repellents exhibit superior repellency on somesubstrates or require higher loading levels.

The present invention further comprises substrates treated with thefluorinated amide-containing fluorinated copolymer solution of Formula 1of the present invention. Suitable substrates include fibrous or hardsurface substrates. The fibrous substrates include woven and nonwovenfibers, fabrics, fabric blends, textiles, nonwovens, paper, leather, andcarpets. These are made from natural or synthetic fibers includingcotton, cellulose, wool, silk, polyamide, polyester, polyolefin,polyacrylonitrile, polypropylene, rayon, nylon, aramid, and acetate orblends thereof. By “fabric blends” is meant fabric made of two or moretypes of fibers. Typically these blends are a combination of at leastone natural fiber and at least one synthetic fiber, but also can includea blend of two or more natural fibers or of two or more syntheticfibers. These substrates are often used in a wide variety of usesincluding, for example, textiles, clothing, furnishings, and carpets.The hard surface substrates include porous and non-porous mineralsurfaces, such as glass, stone, masonry, concrete, unglazed tile, brick,porous clay and various other substrates with surface porosity. Specificexamples of such substrates include unglazed concrete, brick, tile,stone (including granite and limestone), grout, mortar, marble,limestone, statuary, monuments, wood, composite materials such asterrazzo, and wall and ceiling panels including those fabricated withgypsum board. These are used in the construction of buildings, roads,parking ramps, driveways, floorings, fireplaces, fireplace hearths,counter tops, and other decorative uses in interior and exteriorapplications. The substrates of the present invention have excellentwater repellency and oil repellency.

The fluorinated amide-containing copolymer compositions of the presentinvention having a perfluoroalkyl chain of 1 to about 20 carbons areuseful to provide one or more of excellent water repellency and oilrepellency to treated substrates. The fluorinated amide-containingcopolymers of the present invention allow for the use of shorterperfluoroalkyl groups containing 6 or fewer carbon atoms whileconventional commercially available acrylates typically show poor oilrepellency and water repellency performance if the perfluoroalkyl groupscontain less 8 carbon atoms.

MATERIALS AND TEST METHODS

Tetrahydrofuran (THF) and stearyl methacrylate (SMA) were obtained fromSigma-Aldrich, St. Louis, Mo. THF is used in the Examples herein todesignate tetrahydrofuran.

Perfluoro-2-methyl-3-oxahexanoyl fluoride and CF₃(OCF₂)_(n)CO₂CH₃ wereobtained from E. I. du Pont de Nemours and Company, Wilmington, Del.

Cotton fabric was 100% Levi's cotton (medium tan) from INVISTA,Wilmington, Del.

100% Nylon fabric was from Burlington Industries (ITG), Greensboro, N.C.

Test Method 1—Fibrous Substrate Treatment

The fibrous substrate, for example fabric, was treated with thecopolymer dispersion or solution using a following process. Copolymersolutions were prepared in tetrahydrofuran to contain 2000 mg/kg offluorine. The solutions were applied to cotton and nylon substrates bypipetting the copolymer solution the substrates to saturation. Afterapplication, the substrate was dried in air and cured at approximately150° C. for about 2 minutes. The substrate was allowed to cool down toroom temperature before the oil and water repellency measurements wereconducted.

Test Method 2—Water Repellency

The water repellency of a treated substrate was measured according toAATCC standard Test Method No. 193-2004 and the DuPont TechnicalLaboratory Method as outlined in the TEFLON Global Specifications andQuality Control Tests information packet. The test determines theresistance of a treated substrate to wetting by aqueous liquids. Dropsof water-alcohol mixtures of varying surface tensions are placed on thesubstrate and the extent of surface wetting is determined visually. Thetest provides a rough index of aqueous stain resistance.

The composition of water repellency test liquids is shown in table 1.

TABLE 1 Water Repellency Test Liquids Water Repellency Composition, Vol% Rating Number Isopropyl Alcohol Distilled Water 1 2 98 2 5 95 3 10 904 20 80 5 30 70 6 40 60 7 50 50 8 60 40 9 70 30 10 80 20 11 90 10 12 1000

Testing Procedure:

Three drops of Test Liquid 1 are placed on the treated substrate. After10 seconds, the drops are removed by using vacuum aspiration. If noliquid penetration or partial absorption (appearance of a darker wetpatch on the substrate) is observed, the test is repeated with TestLiquid 2. The test is repeated with Test Liquid 3 and progressivelyhigher Test Liquid numbers until liquid penetration (appearance of adarker wet patch on the substrate) is observed. The test result is thehighest Test Liquid number that does not penetrate into the substrate.Higher scores indicate greater repellency.

Test Method 3—Oil Repellency

The treated fabric samples were tested for oil repellency by amodification of AATCC standard Test Method No. 118, conducted asfollows. A fabric sample is treated with a polymer solution aspreviously described. A series of organic liquids, identified below inTable 2, are then applied drop wise to the fabric samples. Beginningwith the lowest numbered test liquid (Repellency Rating No. 1), one drop(approximately 5 mm in diameter or 0.05 mL volume) is placed on each ofthree locations at least 5 mm apart. The drops are observed for 30seconds. If, at the end of this period, two of the three drops are stillspherical in shape with no wicking around the drops, three drops of thenext highest numbered liquid are placed on adjacent sites and similarlyobserved for 30 seconds. The procedure is continued until one of thetest liquids results in two of the three drops failing to remainspherical to hemispherical, or wetting or wicking occurs.

The oil repellency rating of the fabric is the highest numbered testliquid for which two of the three drops remained spherical tohemispherical, with no wicking for 30 seconds. In general, treatedfabrics with a rating of 5 or more are considered good to excellent;fabrics having a rating of one or greater can be used in certainapplications.

The treated samples of hard surface substrates were tested for oilrepellency by a modification of AATCC standard Test Method No. 118,conducted as follows. Three drops of Test Oil 1 in Table 2 are placed onthe treated substrate. After 30 s, the drops are removed by using vacuumaspiration. If no liquid penetration or partial absorption (appearanceof a darker wet patch on the substrate) is observed, the test isrepeated with Test Oil 2. The test is repeated with Test Oil 3 andprogressively higher Test Oil numbers until liquid penetration(appearance of a darker wet patch on the substrate) is observed. Thetest result is the highest Test Oil number that does not show liquidpenetration into the substrate. Higher scores indicate greaterrepellency.

TABLE 2 Oil Repellency Test Liquids Oil Repellency Rating Number TestSolution 1 NUJOL Purified Mineral Oil 2 65/35 NUJOL/n-hexadecane byvolume at 21° C. 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane7 n-octane 8 n-heptane Note: NUJOL is a trademark of Plough, Inc., for amineral oil having a Saybolt viscosity of 360/390 s at 38° C. and aspecific gravity of 0.880/0.900 at 15° C.

EXAMPLES Example 1

A 50-mL flask was charged with methyl2,2,3,3-tetrahydroperfluorononanoate (9.0 g, prepared according to theprocedure in U.S. Pat. No. 6,054,615) and 1,3-diamino-2-propanol (1.0g). The resulting mixture was allowed to stir at 140° C. for 8 h. Thereaction mixture solidified after being cooled to room temperature anddried on full vacuum for 8 h to give a solid (8.95 g). The product wasN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propanol asshown by the following analyses. H NMR (CDCl₃) 2.52 (m, 9H), 3.36 (m,4H), 3.80 (quintet, J=5 Hz, 1H), 6.36 (br s, 2H) ppm. F NMR −81.2 (tt,J=10, 3 Hz, 6F), −114.9 (m, 4F), −122.3 (m, 4F), −123.3 (m, 4F), −123.9(m, 4F), −126.5 (m, 4F) ppm. For HNMR and FNMR for this and all examplesherein, ppm indicates one part per one million parts in frequency shift.

A 25-mL flask was charged withN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propanol(6.0 g.) prepared according to the above procedure, triethylamine (1.42g), and tetrahydrofuran (20 mL). Methacryloyl chloride (1.45 g) intetrahydrofuran (3 mL) was added drop wise to the above mixture at about10° C. The mixture was stirred at room temperature for 15 h. The mixturewas poured into water (40 mL) and extracted with ether (2×100 mL). Theether solution was washed with water (3×50 mL), Saturated NaCl solution(10 mL), dried over Na₂SO₄, concentrated, and dried on vacuum to give6.35 g wax product. The product isN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propylmethacrylate.

A mixture ofN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propylmethacrylate (2.0 g), stearyl methacrylate (0.8 g),2,2′-azobis(2,4-dimethylpentanenitrile) (VAZO 52) (25 mg), andtetrahydrofuran (5 mL) was heated to 60° C. for 15 h. The mixture waspoured into methanol (100 mL). The precipitated polymer was washed withmethanol (2×30 mL), dried on vacuum to give a polymer (1.28 g). It was acopolymer and contained about 38.7% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 2

A 100-mL bottle was charged with diethylenetriamine (6.64 g) and 52.6 gof methyl 2,2,3,3-tetrahydroperfluorononanoate (prepared according aprocedure from U.S. Pat. No. 6,054,615). The resulting mixture washeated to 120° C. for 20 h. The reaction mixture was dried on vacuum at70° C. for 2 h to give a solid (54 g). The product is1,7-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,4,7-triazaheptane asshown by the following analyses. H NMR (CDCl₃): 1.66 (br s, 1H), 2.51(m, 8H), 2.78 (t, J=6 Hz, 4H), 3.35 (q, J=6 Hz, 4H), 6.20 (br s, 2H)ppm. F NMR (CDCl₃): −81.3 (tt, J=10, 3 Hz, 6F), −115.1 (m, 4F), −122.4(m, 4F), −123.4 (m, 4F), −124.0 (m, 4F), −126.6 (m, 4F) ppm.

A 100-mL flask was charged with1,7-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,4,7-triazaheptane (15.7g), triethylamine (2.49 g), and tetrahydrofuran (22 mL). Methacryloylchloride (2.58 g dissolved in 7 mL of tetrahydrofuran) was added dropwise to the above mixture at about 10° C. The mixture was stirred atroom temperature for 2 h. The reaction mixture was poured into water(200 mL) and extracted with methylene chloride (250 mL). The methylenechloride extract was washed with water (3×50 mL). The original aqueouslayer was extracted with ether (200 mL) and this ether extract waswashed with water (3×50 mL) and saturated NaCl solution. The combinedmethylene chloride and solution were dried over Na₂SO₄, concentrated,and dried on vacuum to give a solid (14.8 g). The product is1,7-bis(2,2,3,3-tetrahydroperfluorononanoyl)-4-methacryloyl-1,4,7-triazaheptaneas shown by the following analyses. H NMR (CDCl₃): 1.89 (m, 3H), 2.51(m, 8H), 3.55 (m, 8H), 4.90 (m, 1H), 5.16 (m, 1H), 6.31 (br s, 1H), 7.51(br s, 1H) ppm. F NMR (CDCl₃): −81.3 (t, J=10 Hz, 6F), −115.1 (m, 4F),−122.4 (m, 4F), −123.4 (m, 4F), −124.0 (m, 4F), −126.6 (m, 4F) ppm.

A mixture of stearyl methacrylate (1.6 g),1,7-bis(2,2,3,3-tetrahydroperfluorononanoyl)-4-methacryloyl-1,4,7-triazaheptane(4.0 g), tetrahydrofuran (10 mL), and2,2′-azobis(2,4-dimethylpentanenitrile) (45 mg) was heated to 60° C. for36 h. The mixture was poured into methanol (100 mL). The precipitatedpolymer was washed with methanol (2×30 mL), dried on vacuum to give asolid (1.85 g). It was a copolymer and contained about 9.4% fluorine.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 3

A 25-mL bottle was charged with 1,3-diamino-2-propanol (0.61 g) andtetrahydrofuran (4 mL). Ethyl 3,3,4,4-tetrahydroperfluorooctanoate (5.0g), (prepared according a procedure from U.S. Pat. No. 6,376,705), intetrahydrofuran (2 mL) was added drop wise at about 10° C. The resultingmixture was allowed to stir for 15 h at room temperature. The reactionmixture was concentrated and dried on vacuum to give 5.0 g of solid. Theproduct isN,N′-bis(3,3,4,4-tetrahydroperfluorooctanoyl)-1,3-diamino-2-propanol asshow by the following analyses. H NMR (CDCl₃) 1.53 (br s, 1H), 2.41 (m,8H), 3.45 (m, 4H), 3.97 (Quintet, J=5 Hz, 1H), 6.99 (br. s, 2H) ppm. FNMR −81.5 (tt, J=10, 3 Hz, 6F), −107.1 (m, 4F), −115.1 (m, 4F), −124.7(m, 4F), −126.4 (m, 4F) ppm.

A 50-mL flask was charged withN,N′-bis(3,3,4,4-tetrahydroperfluorooctanoyl)-1,3-diamino-2-propanol(4.8 g) prepared according to the above procedure, triethylamine (0.80g), and tetrahydrofuran (20 mL). Methacryloyl chloride (0.82 g) intetrahydrofuran (3 mL) was added drop wise to the above mixture at roomtemperature. The mixture was stirred at room temperature for 15 h. GCanalysis of the reaction mixture indicated the formation of the productand about 4% of starting alcohol. Methacryloyl chloride (0.1 g) andtriethylamine (0.10 g) were added to the reaction mixture. The resultingmixture was stirred at 35° C. for another 15 h. The reaction mixture wasconcentrated and dried on vacuum to give 5.0 g of solid. The product isN,N′-bis(3,3,4,4-tetrahydroperfluorooctanoyl)-1,3-diamino-2-propylmethacrylate as shown by the following analyses. H NMR(tetrahydrofuran-d8) 2.00 (m, 3H), 2.54 (m, 8H), 3.60 (m, 4H), 5.26 (m,1H), 5.69 (m, 1H), 6.19 (m, 1H), 8.45 (br. s, 2H) ppm. F NMR −81.5 (tt,J=10, 3 Hz, 6F), −106.9 (ABq t, J=258, 15 Hz, 4F), −114.7 (m, 4F),−124.2 (m, 4F), −126.1 (m, 4F) ppm.

A mixture ofN,N′-bis(3,3,4,4-tetrahydroperfluorooctanoyl)-1,3-diamino-2-propylmethacrylate (2.0 g), stearyl methacrylate (0.80 g),2,2′-azobis(2,4-dimethylpentanenitrile) (25 mg), and tetrahydrofuran (5mL) was heated to 60° C. for 15 h. The mixture was poured into methanol(100 mL). The precipitated polymer was washed with methanol (2×30 mL),dried on vacuum to give a white solid (2.44 g). It was a copolymer andcontained about 44.6% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 4

A 25-mL bottle was charged with diethylenetriamine (0.85 g) andtetrahydrofuran (4 mL). Ethyl 3,3,4,4-tetrahydroperfluorooctanoate (6.25g, prepared according a procedure from U.S. Pat. No. 6,376,705), intetrahydrofuran (2 mL) was added drop wise at about 10° C. The resultingmixture was allowed to stir for 15 h at room temperature. The reactionmixture was concentrated and dried on vacuum to give 6.27 g of solid.The product is1,7-bis(2,2,3,3-tetrahydroperfluorooctanoyl)-1,4,7-triazaheptane asshown by the following analyses. H NMR (CDCl₃) 1.55 (br s, 1H), 2.39 (m,8H), 2.85 (t, J=6 Hz, 4H), 3.42 (q, J=6 Hz, 4H), 6.80 (br. s, 2H) ppm. FNMR −81.5 (tt, J=10, 3 Hz, 6F), −107.3 (t, J=16 Hz, 4F), −115.2 (m, 4F),−124.8 (m, 4F), −126.5 (m, 4F) ppm.

A 25-mL flask was charged with1,7-bis(2,2,3,3-tetrahydroperfluorooctanoyl)-1,4,7-triazaheptane (3 g),triethylamine (0.49 g), and tetrahydrofuran (5 mL). Methacryloylchloride (0.50 g) in tetrahydrofuran (2 mL) was added drop wise to theabove mixture at about 10° C. The mixture was stirred at roomtemperature for 3 h. The reaction mixture was pored into water (40 mL)and extracted with methylene chloride (50 mL). The organic layer waswashed with water (2×30 mL), dried over Na₂SO₄, concentrated and driedon vacuum to give a wax product (3.3 g). The product is1,7-bis(2,2,3,3-tetrahydroperfluorooctanoyl)-4-methacryloyl-1,4,7-triazaheptaneas shown by the following analyses. H NMR (CDCl₃) 1.93 (s, 3H), 2.38 (m,8H), 3.57 (m, 4H), 3.62 (m, 4H), 5.01 (m, 1H), 5.22 (m, 1H), 6.23 (br.s, 2H) ppm. F NMR −81.5 (tt, J=10, 3 Hz, 6F), −107.3 (m, 4F), −115.2 (m,4F), −124.7 (m, 4F), −126.5 (m, 4F) ppm.

A mixture of1,7-bis(2,2,3,3-tetrahydroperfluorooctanoyl)-4-methacryloyl-1,4,7-triazaheptane(2.0 g), stearyl methacrylate (0.8 g),2,2′-azobis(2,4-dimethylpentanenitrile) (25 mg), and tetrahydrofuran (3mL) was heated to 60° C. for 15 h. The mixture was poured into methanol(100 mL). The precipitated polymer was washed with methanol (2×30 mL),dried on vacuum to give a white solid (0.85 g). It was a copolymer andcontained about 5.1% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 5

A 25-mL bottle was charged with 1,3-diamino-2-propanol (0.5 g) andtetrahydrofuran (2 mL). Ethyl 3,3,4,4-tetrahydroperfluorodecanoate (5.45g), (prepared according a procedure from U.S. Pat. No. 6,376,705), intetrahydrofuran (2 mL) was added drop wise at about 15° C. The resultingmixture was allowed to stir for 3 hours at room temperature then at 50°C. for 2 h. The reaction mixture was concentrated and dried on vacuum togive 5.08 g of white solid, yield about 96%. The product isN,N′-bis(3,3,4,4-tetrahydroperfluorodecanoyl)-1,3-diamino-2-propanol asshown by the following analyses. H NMR 2.49 (m, 8H), 2.78 (br s, 1H),3.37 (m, 4H), 3.95 (quintet, J=6 Hz, 1H), 8.07 (br s, 2H) ppm. F NMR−82.2 (tt, J=10, 3 Hz, 6F), −107.9 (m, 4F), −115.3 (m, 4F), −122.9 (m,4F), −123.8 (m, 4F), −124.2 (m, 4F), −127.2 (m, 4F) ppm.

A 25-mL flask was charged withN,N′-bis(3,3,4,4-tetrahydroperfluorodecanoyl)-1,3-diamino-2-propanol(2.0 g), triethylamine (0.33 g), and tetrahydrofuran (3 mL).Methacryloyl chloride (0.33 g) in tetrahydrofuran (3 mL) was added dropwise at about 10° C. The resulting mixture was allowed to stir for 15 hat room temperature. The resulting solids were removed by filtration andwashed with about 50 mL of methylene chloride. The combined filtrate andwashings were then poured into about 25 mL water. The organic layer wasisolated and washed again with water (2×30 mL), dried over Na₂SO₄,concentrated, and dried under vacuum over night to give a solid (2.03g). The product isN,N′-bis(3,3,4,4-tetrahydroperfluorodecanoyl)-1,3-diamino-2-propylmethacrylate as shown by the following analyses. F NMR (acetone-d6)-82.2(tt, J=10, 3 Hz, 6F), −107.8 (ABq m, J=255 Hz, 4F), −122.9 (m, 4F),−123.8 (m, 4F), −124.2 (m, 4F), −127.2 (m, 4F) ppm. H NMR (acetone-d6)1.89 (m, 3H), 2.47 (m, 8H), 3.36 (m, 4H), 5.22 (m, 1H), 5.62 (m, 1H),6.08 (m, 1H), 8.39 (br s, 2H) ppm.

A mixture ofN,N′-bis(3,3,4,4-tetrahydroperfluorodecanoyl)-1,3-diamino-2-propylmethacrylate (2.0 g), stearyl methacrylate (1.2 g),2,2′-azobis(2,4-dimethylpentanenitrile) (25 mg), and tetrahydrofuran (10mL) was heated at 60° C. for 15 h. The reaction mixture was poured intomethanol (80 mL). The polymer was precipitated and washed with methanol(20 mL), then dried on vacuum to give a white solid (2.36 g). It was acopolymer and contained about 34% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 6

A 25-mL bottle was charged with diethylenetriamine (1.1 g) andtetrahydrofuran (5 mL). Ethyl 3,3,4,4-tetrahydroperfluorodecanoate (10g, prepared according a procedure from U.S. Pat. No. 6,376,705) intetrahydrofuran (4 mL) was added drop wise at about 15° C. The resultingmixture was allowed to stir for 15 h at room temperature. The reactionmixture was concentrated and dried on vacuum to give 10 g of solid. Theproduct is1,7-bis(2,2,3,3-tetrahydroperfluorodecanoyl)-1,4,7-triazaheptane asshown by the following analyses. H NMR (CDCl₃) 1.28 (br s, 1H), 2.39 (m,8H), 2.85 (t, J=5 Hz, 4H), 3.42 (q, J=5 Hz, 4H), 6.79 (br. s, 2H) ppm. FNMR −81.3 (tt, J=10, 3 Hz, 6F), −107.4 (t, J=16 Hz, 4F), −115.0 (m, 4F),−122.4 (m, 4F), −123.3 (m, 4F), −123.8 (m, 4F), −126.6 (m, 4F) ppm.

A 25-mL flask was charged with1,7-bis(2,2,3,3-tetrahydroperfluorodecanoyl)-1,4,7-triazaheptane (5 g),triethylamine (0.64 g), and tetrahydrofuran (15 mL). Methacryloylchloride (0.67 g) in tetrahydrofuran (3 mL) was added drop wise to theabove mixture at about 10° C. The mixture was stirred at roomtemperature for 15 h. The reaction mixture was poured into water (50 mL)and extracted with methylene chloride (100 mL). The organic layer waswashed with water (2×50 mL). During second wash, the organic layerbecame gel. The gel was isolated and dried in air to give 4.9 g solid.The product is1,7-bis(2,2,3,3-tetrahydroperfluorodecanoyl)-4-methacryloyl-1,4,7-triazaheptaneas shown by the following analyses. H NMR (THF-d8) 2.00 (m, 3H), 2.52(m, 8H), 3.55 (m, 4H). 3.67 (m, 4H), 5.12 (m, 1H), 5.23 (m, 1H), 8.41(br s, 2H) ppm. F NMR (THF-d8) −81.5 (tt, J=10 Hz, 6F), −107.2 (m, 4F),−114.8 (m, 4F), −122.2 (m, 4F), −123.1 (m, 4F), −123.6 (m, 4F), −126.5(m, 4F) ppm.

A mixture of1,7-bis(2,2,3,3-tetrahydroperfluorodecanoyl)-4-methacryloyl-1,4,7-triazaheptane(2.0 g), stearyl methacrylate (0.8 g),2,2′-azobis(2,4-dimethylpentanenitrile) (25 mg), and tetrahydrofuran (3mL) were heated to 60° C. for 24 h. The reaction mixture was poured intomethanol (100 mL). The precipitated polymer was washed with methanol(2×30 mL) and dried under vacuum to give a white solid (0.81 g). It wasa copolymer and contained about 5.6% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 7

A mixture ofN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propylacrylate (2.0 g), stearyl methacrylate (0.8 g),2,2′-azobis(2,4-dimethylpentanenitrile) (35 mg), and tetrahydrofuran (5mL) was heated to 60° C. for 15 h. The mixture was poured into methanol(100 mL). The precipitated polymer was washed with methanol (2×20 mL)and dried on vacuum to give a solid (2.48 g). It was a copolymer andcontained about 32.7% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 8

A mixture ofN,N′-bis(2,2,3,3-tetrahydroperfluorononanoyl)-1,3-diamino-2-propylmethacrylate (1.8 g), styrene (0.88 g),2,2′-azobis(2,4-dimethylpentanenitrile) (25 mg), and tetrahydrofuran (5mL) was heated to 60° C. for 15 h. The mixture was poured into methanol(100 mL). The precipitated polymer was washed with methanol (2×30 mL),dried on vacuum to give a solid (1.56 g). It was a copolymer andcontained about 38% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 9

A 25-mL flask was charged with 1,3-diamino-2-propanol (1.5 g) and THF (5mL). CF₃(OCF₂)_(n)CO₂Me (n: 2-5, 14.5 g) in THF (5 mL) was added dropwise at about 10° C. The resulting mixture was allowed to stir for 15 hat room temperature. The reaction mixture was concentrated and dried onvacuum to give 13.5 g of viscous oil, having H NMR (CDCl₃) 1.55 (br s,1H), 3.41 (m, 4H), 4.02 (Quintet, J=5 Hz, 1H), 6.95 (br. s, 2H) ppm. Theproduct is N,N′-bis(polyoxaperfluoroacyl)-1,3-diamino-2-propanol.

A 25-mL flask was charged withN,N′-bis(polyoxaperfluoroacyl)-1,3-diamino-2-propanol (5.5 g,E110448-72), Et₃N (0.82 g), and THF (15 mL). Methacryloyl chloride (0.84g in 3 mL of THF) was added drop wise to the above mixture at about 10°C. The mixture was stirred at room temperature for 15 h. GC analysis ofthe reaction mixture indicated the formation of the product. The mixturewas poured into water (40 mL) and extracted with ether (100 mL). Theether solution was washed with water (3×30 mL), NaCl (saturated, 10 mL),dried over Na₂SO₄, concentrated and dried on vacuum to give 5.7 g of avery viscous oil. The product isN,N′-bis(polyoxaperfluoroacyl)-1,3-diamino-2-propyl methacrylate.

A mixture of N,N′-bis(polyoxaperfluoroacyl)-1,3-diamino-2-propylmethacrylate (2.0 g), stearyl methacrylate (0.80 g), VAZO 52 (25 mg),and THF (5 mL) was heated to 60° C. for 15 h. The mixture was pouredinto methanol (100 mL). The precipitated polymer was washed withmethanol (2×30 mL), dried under vacuum to give a white solid (1.01 g).It was a copolymer and contained about 23.7% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 10

A 100-mL flask was charged with ethanolamine (2.0 g) and THF (20 mL).CF₃(OCF₂)_(n)CO₂Me (n: 2-5, 10 g) was added drop wise to the abovemixture at room temperature. A slightly exothermic reaction wasobserved. The mixture was stirred at room temperature for 1 h. GCanalysis of the mixture indicated that the desired amides were formed.The reaction mixture was allowed to stir at room temperature over night.The reaction mixture was poured into water (150 mL) and extracted withCH₂Cl₂ (100 mL). The extract was washed with water (3×50 mL) andconcentrated, dried on vacuum to give an oil (9.5 g), having H NMR(CDCl₃) 1.77 (br s, 1H), 3.54 (q, J=5 Hz, 2H), 3.92 (t, J=5 Hz, 2H),6.74 (br s, 1H) ppm. The product isN-(polyoxaperfluoroacyl)-2-aminoethanol.

A 100-mL flask was charged with triethylamine (3.0 g), THF (60 mL), andN-(polyoxaperfluoroacyl)-2-aminoethanol (9.1 g). Methacryloyl chloride(3.1 g in THF 20 mL) was added drop wise to the above mixture at 10° C.The mixture was stirred at room temperature for 3 h. The solid wasremoved by filtration and the filtrate was poured into water (150 mL)and extracted with CH₂Cl₂ (2×100 mL). The extracts were washed withwater (3×50 mL) and concentrated, dried on vacuum to give oil (10.3 g).It is N-(polyoxaperfluoroacyl)-2-aminoethyl methacrylate.

In a dry box, a 25-mL flask was charged with VAZO 52 (25 mg), THF (5mL), stearyl methacrylate (1.0 g), andN-(polyoxaperfluoroacyl)-2-aminoethyl methacrylate (2.0 g). The mixturewas heated to 60° C. for 15 h. The reaction mixture became very viscousand was poured into MeOH (50 mL). The precipitated polymer was washedwith MeOH (2×20 mL) and dried under vacuum to give a solid (2.5 g). Itwas a copolymer and contained about 23.5% F by NMR.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Example 11

A mixture of ethanolamine (13 g, 28 mmole) and ether (30 mL) was cooledto 15° C. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33 g in ether 50mL) was added dropwise to keep the reaction temperature below 25° C.After the addition, the reaction mixture was stirred at room temperaturefor one hour. The solid was removed by filtration and the filtrate waswashed with hydrochloric acid (0.5N, 30 mL), water (2 times 30 mL),sodium hydrogen carbonate solution (0.5N, 20 mL), water (30 mL), andsodium chloride solution (saturated, 20 mL). It was then concentratedand dried in vacuum over night at room temperature to give a white solid35 g, yield 95%. H NMR (CDCl₃) 1.67 (br s, 1H), 3.57 (m, 2H), 3.80 (t,J=5 Hz, 2H), 6.91 (br s, 1H) ppm. F NMR (CDCl₃) −81.2 (dm, J=148 Hz,1F), −81.7 (t, J=7 Hz, 3F), −82.7 (d, J=3 Hz, 3F), −85.2 (dm, J=148 Hz,1F), −130.1 (s, 2F), −133.2 (m, 1F) ppm. The product isN-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethanol.

A 250-mL flask was charged with triethylamine (8.2 g), THF (80 mL), andN-(perfluoro-2-methyl-3-oxo-hexanoyl)-2-aminoethanol (25 g).Methacryloyl chloride (8.44 g in tetrahydrofuran, 20 mL) was addeddropwise to the above mixture at 5° C. The mixture was stirred at roomtemperature overnight. The reaction mixture was poured into water (200mL) and two layers were formed. The aqueous layer (top layer) wasextracted with methylene chloride (five time 50 mL). The combinedmethylene chloride extracts and original organic layer were washed withwater (six times 60 mL), neutralized with dilute hydrochloric acid(0.5N), dried over anhydrous sodium sulfate, concentrated and dried onvacuum to give a oil, N-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethylmethacrylate (27.06 g), yield 92%. H NMR (CDCl₃) 1.94 (m, 3H), 3.72 (m,2H), 4.33 (m, 2H), 5.63 (m, 1H), 6.12 (m, 1H), 6.88 (br s, 1H) ppm. FNMR (CDCl₃) −81.2 (dm, J=148 Hz, 1F), −81.7 (t, J=7 Hz, 3F), −82.7 (d,J=3 Hz, 3F), −85.2 (dm, J=148 Hz, 1F), −130.1 (s, 2F), −133.4 (m, 1F)ppm.

In a dry box, a mixture of VAZO 52 (47 mg), THF (5 mL), stearylmethacrylate (1.91 g), andN-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethyl methacrylate (2.48 g)was heated to 60° C. for 17 hours. The reaction mixture was poured intomethanol (60 mL) and the precipitated polymer was washed with methanoland dried on vacuum to give a solid 3.72 g. It was a copolymer ofN-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethyl methacrylate andstearyl methacrylate and contained 22% F. A solution of the copolymerwas prepared and was applied to cotton and nylon fabric using theprocedure of Test Method 1. The treated fabric was tested for waterrepellency and oil repellency using Test Methods 2 and 3, respectively.The results are in Table 3.

Comparative Example A

Under a nitrogen atmosphere charged a 20 mL vial with1H,1H,2H,2H-perfluorooctylacrylate (2.0 g), obtained from SynQuestFluorochemicals (Alachua, Fla.), stearyl methacrylate (1.2 g),tetrahydrofuran (8 mL), and 2,2′-azobis(2,4-dimethylpentanenitrile) (23mg). The reaction was heated at 60° C. for 21 h. After being cooled toroom temperature, the reaction mixture was poured into methanol (100mL). The precipitated polymer was washed with methanol (20 mL) and driedunder vacuum to give polymer (2.56 g).

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively. The results are in Table 3.

Comparative Example B

A 250-mL flask was charged with 1H,1H,2H,2H-perfluorodecyl acrylateobtained from SynQuest Fluorochemicals (Alachua, Fla.) (20.4 g), stearylmethacrylate (13.5 g), 1-dodecanethiol (0.2 g),2,2′-azobis(2-methylbutyronitrile, (VAZO 67, 0.4 g), and tetrahydrofuran(100 mL). The flask was cooled to 18° C. and flushed with nitrogen for30 min. The reaction mixture was heated for 14.5 h at 66° C. using a 75°C. oil bath. A reaction mixture (115.4 g) was obtained. Its solidcontent was determined by the following procedure: a sample (1.82 g) ofthe reaction solution was dried under vacuum at 80° C. to give a solid,0.56 g.

A solution of the copolymer was prepared and was applied to cotton andnylon fabric using the procedure of Test Method 1. The treated fabricwas tested for water repellency and oil repellency using Test Methods 2and 3, respectively.

The results are in Table 3.

TABLE 3 On Cotton On Nylon Oil Water Oil Water Example RepellencyRepellency Repellency Repellency 1 2 4 5 7 2 0 3 5 5 3 1 3 2 7 4 2 2 6 55 4 7 5 7 6 0 4 2 7 7 3 4 5 7 8 3 7 5 9 9 2 5 4 7 10 2 6 2 6 11 1 5 3 7Comparative A 0 0 0 4 Comparative B 0 4 0 7

The data in Table 3 demonstrated the Examples are comparable or betterthan the prior art. For cotton, Examples 3 and 4 had a perfluoroalkylchain length of 4 carbons, so this represents the lower limit for waterrepellency but provided superior oil repellency. For nylon, ComparativeExample B had 8 carbons in the perfluoroalkyl chain, and for waterrepellency the Examples of the present invention having 4 or 6 carbonswere comparable. For nylon, the Examples of the present invention weresuperior for oil repellency.

1. (canceled)
 2. A composition comprising Formula 2

wherein R_(f) is a linear perfluoroalkyl group having from about 1 toabout 20 carbon atoms, or a mixture thereof, which is optionallyinterrupted by at least one oxygen atom, X³ is oxygen or X¹, each X¹ isindependently an organic divalent linking group having from about 1 toabout 20 carbon atoms, optionally containing an oxygen, nitrogen, orsulfur, or a combination thereof, G is F or CF₃, A is an amide, j iszero or positive integer, provided that when Y is N, j is a positiveinteger, X² is an organic linking group, Y is O, N or S, h is zero whenY is N, and h is one when Y is O or S, Z is H, a straight or branchedalkyl group having from about 1 to about 4 carbon atoms, or halide, andB is H or

wherein R_(f), X¹, X³, G, A, and j are as defined above.
 3. Acomposition comprising Formula 3

wherein R_(f) is a linear perfluoroalkyl group having from about 1 toabout 20 carbon atoms, or a mixture thereof, which is optionallyinterrupted by at least one oxygen atom, X³ is oxygen or X¹, each X¹ isindependently an organic divalent linking group having from about 1 toabout 20 carbon atoms, optionally containing an oxygen, nitrogen, orsulfur, or a combination thereof, G is F or CF₃, A is an amide, j iszero or positive integer, provided that when Y is N, j is a positiveinteger, X² is an organic linking group, Y is O, N or S, h is zero whenY is N, and h is one when Y is O or S, Z is H, a straight or branchedalkyl group having from about 1 to about 4 carbon atoms, or halide, andB is H or

wherein R_(f), X¹, X³, G, A, and j are as defined above, and E isselected from the group consisting of hydroxyl, amine, halogen andthiol, provided that h is zero when E is amine, and h is one when E isother than amine.
 4. The composition of claim 2 or 3 wherein R_(f) is aperfluoroalkyl group having the formula F(CF₂CF₂)_(n), wherein n is 2 toabout 20, or mixtures thereof.
 5. The composition of claim 4 wherein nis 3 or
 6. 6. The composition of claim 2 or 3 wherein X¹ is selectedfrom the group consisting of a straight chain, branched chain or cyclicalkylene, phenyl, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido,carbonamido, carbonyloxy, urethanylene, ureylene, and combinationsthereof.
 7. The composition of claim 2 or 3 wherein X² is R⁵C wherein R⁵is H or C₁ to C₄ alkyl.
 8. (canceled)
 9. (canceled)
 10. (canceled) 11.(canceled)
 12. A method of providing water repellency and oil repellencyto a substrate comprising contacting said substrate with a compositionof Formula I

wherein R_(f) is a straight or branched perfluoroalkyl group having fromabout 1 to about 20 carbon atoms, or a mixture thereof, which isoptionally interrupted by at least one oxygen atom, X³ is oxygen or X¹,each X¹ is independently an organic divalent linking group having fromabout 1 to about 20 carbon atoms, optionally containing an oxygen,nitrogen, or sulfur, or a combination thereof, G is F or CF₃, A is anamide, j is zero or positive integer, X² is an organic linking group, Yis O, N or S, h is zero when Y is N, and h is one when Y is O or S, Z isH, a straight or branched alkyl group having from about 1 to about 4carbon atoms, or halide, B is H or

wherein R_(f), X¹, X³, G, A, and j are as defined above, m is a positiveinteger, q is zero or a positive integer when Y is O, and q is apositive integer when Y is N or S, p is zero or a positive integer whenY is O, and p is a positive integer when Y is N or S, each W isindependently

or [R¹—X¹—Y—C(O)—C(Z)-CH₂], wherein X¹, Y, and Z are as defined above,Rx is C(O)O(R¹), C(O)N(R²)₂, OC(O)(R¹), SO₂(R¹), C₆(R³)₅, O(R¹), halide,or R¹; each R¹ is independently H, C_(n)H_(2n+1), C_(n)H_(2n)—CH(O)CH₂,[CH₂CH₂O]_(i)R⁴, [C_(n)C_(2n)]N(R⁴)₂ or [C_(n)H_(2n)]C_(n)F_(2n+1), n is1 to 40, R⁴ is H or C_(s)H_(2s+1), s=0 to 40, i=1 to 200, each R² isindependently H, or C_(t)H_(2t+1) wherein t is 1 to 20, each R³ isindependently H, COOR¹, halogen, N(R¹)₂, OR¹, SO₂NHR¹, CH═CH₂, or SO₃M,wherein R¹ is as defined above, and M is H, alkali metal salt, alkalineearth metal salt, or ammonium.
 13. The method of claim 12 wherein thecomposition is applied as an aqueous dispersion or solution.
 14. Themethod of claim 12 wherein the composition is applied by means ofexhaustion, spray, foam, flex-nip, nip, pad, kiss-roll, beck, skein,winch, liquid injection, overflow flood, brush, roll, spray orimmersion.
 15. The method of claim 12 wherein the composition is appliedin the presence of at least one of A) an agent which provides a surfaceeffect which is no iron, easy to iron, shrinkage control, wrinkle free,permanent press, moisture control, softness, strength, anti-slip,antistatic, anti-snag, anti-pill, stain repellency, stain release, soilrepellency, soil release, water repellency, oil repellency, odorcontrol, antimicrobial, or sun protection, B) a surfactant, antioxidant,light fastness agent, color fastness agent, water, pH adjuster, crosslinker, wetting agent, extender, foaming agent, processing aid,lubricant, blocked isocyanate, nonfluorinated and extenders, or C)combinations thereof.
 16. A substrate to which has been applied acomposition of Formula 1

wherein R_(f) is a straight or branched perfluoroalkyl group having fromabout 1 to about 20 carbon atoms, or a mixture thereof, which isoptionally interrupted by at least one oxygen atom, X³ is oxygen or X¹,each X¹ is independently an organic divalent linking group having fromabout 1 to about 20 carbon atoms, optionally containing an oxygen,nitrogen, or sulfur, or a combination thereof, G is F or CF₃, A is anamide, j is zero or positive integer, X² is an organic linking group, Yis O, N or S, h is zero when Y is N, and h is one when Y is O or S, Z isH, a straight or branched alkyl group having from about 1 to about 4carbon atoms, or halide, B is H or

wherein R_(f), X¹, X³, G, A, and j are as defined above, provided thatwhen B is H, j is a positive integer, m is a positive integer, q is zeroor a positive integer when Y is O, and q is a positive integer when Y isN or S, p is zero or a positive integer when Y is O, and p is a positiveinteger when Y is N or S, each W is independently

or [R¹—X¹—Y—C(O)—C(Z)-CH₂], wherein X¹, Y, and Z are as defined above,Rx is C(O)O(R¹), C(O)N(R²)₂, OC(O)(R¹), SO₂(R¹), C₆(R³)₅, O(R¹), halide,or R¹; each R¹ is independently H, C_(n)H_(2n+1), C_(n)H_(2n)—CH(O)CH₂,[CH₂CH₂O]_(i)R⁴, [C_(n)C_(2n)]N(R⁴)₂ or [C_(n)H_(2n)]C_(n)F_(2n+1), n is1 to 40, R⁴ is H or C_(s)H_(2s+1), s=0 to 40, i=1 to 200, each R² isindependently H, or C_(t)H_(2t+1) wherein t is 1 to 20, each R³ isindependently H, COOR¹, halogen, N(R¹)₂, OR¹, SO₂NHR¹, CH═CH₂, or SO₃M,wherein R¹ is as defined above, and M is H, alkali metal salt, alkalineearth metal salt, or ammonium.
 17. The substrate of claim 16 which is afibrous substrate.
 18. The substrate of claim 17 which is a fiber, yarn,fabric, fabric blend, textile, nonwoven, carpet, paper or leather. 19.The substrate of claim 17 which is selected from the group consisting ofa polyamide, nylon, wool, polyester, polyolefin, polyaramid, acrylic,wool, cotton, jute, sisal, sea grass, coir, and blends thereof.